Reduction Behavior of Cubic In2O3 Nanoparticles by Combined Multiple In Situ Spectroscopy and DFT,The Journal of Physical Chemistry Letters

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Reduction Behavior of Cubic In2O3 Nanoparticles by Combined Multiple In Situ Spectroscopy and DFT
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2021-04-12 , DOI: 10.1021/acs.jpclett.1c00892
Marc Ziemba ₁ , Leon Schumacher ₁ , Christian Hess ₁

Affiliation

Indium oxide (In₂O₃) has emerged as a highly active catalyst for methanol synthesis by CO₂ hydrogenation. In this work we elucidate the reduction behavior and oxygen dynamics of cubic In₂O₃ nanoparticles by in situ Raman and UV–vis spectra in combination with density functional theory (DFT) calculations. We demonstrate that application of UV and visible Raman spectroscopy enables, first, a complete description of the In₂O₃ vibrational structure fully consistent with theory and, second, the first theoretical identification of the nature of defect-related bands in reduced In₂O₃. Combining these findings with quasi in situ XPS and in situ UV–vis measurements allows the temperature-dependent structural dynamics of In₂O₃ to be unraveled. While the surface of a particle is not in equilibrium with its bulk at room temperature, oxygen exchange between the bulk and the surface occurs at elevated temperatures, leading to an oxidation of the surface and an increase in oxygen defects in the bulk. Our results demonstrate the potential of combining different in situ spectroscopic methods with DFT to elucidate the complex redox behavior of In₂O₃ nanoparticles.

中文翻译：

多重原位光谱和DFT相结合的方法对Cu ₂ In ₃ O ₃纳米粒子的还原行为

氧化铟（In ₂ O ₃）已成为通过CO ₂加氢合成甲醇的高活性催化剂。在这项工作中，我们通过原位拉曼光谱和UV-vis光谱结合密度泛函理论（DFT）计算来阐明立方In ₂ O ₃纳米粒子的还原行为和氧动力学。我们证明了紫外线和可见拉曼光谱的应用首先可以对In ₂ O ₃振动结构进行完整的描述，这与理论完全一致，其次，可以对还原的In ₂ O中与缺陷相关的带的性质进行第一个理论鉴定₃。将这些发现与准原位XPS和原位UV-vis测量相结合，可以揭示In ₂ O ₃随温度变化的结构动力学。尽管颗粒的表面在室温下与其本体不平衡，但是本体和表面之间的氧交换在升高的温度下发生，导致表面的氧化和本体中氧缺陷的增加。我们的结果证明了将不同的原位光谱方法与DFT结合以阐明In ₂ O ₃纳米颗粒的复杂氧化还原行为的潜力。

更新日期：2021-04-22

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